TWI797093B - 蝕刻液組成物及蝕刻方法 - Google Patents
蝕刻液組成物及蝕刻方法 Download PDFInfo
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- TWI797093B TWI797093B TW106136173A TW106136173A TWI797093B TW I797093 B TWI797093 B TW I797093B TW 106136173 A TW106136173 A TW 106136173A TW 106136173 A TW106136173 A TW 106136173A TW I797093 B TWI797093 B TW I797093B
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- Prior art keywords
- etching
- copper
- mass
- acid
- width
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- 238000005530 etching Methods 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 17
- 239000010949 copper Substances 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003851 azoles Chemical class 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000007547 defect Effects 0.000 abstract description 13
- 229920002120 photoresistant polymer Polymers 0.000 description 12
- -1 copper are dissolved Chemical class 0.000 description 11
- 239000000758 substrate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002738 chelating agent Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 6
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 229910003336 CuNi Inorganic materials 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 150000003385 sodium Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
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- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229940045996 isethionic acid Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229960003080 taurine Drugs 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PVPTUASRAVWKGX-UHFFFAOYSA-N 1,2-dihydrotriazol-3-amine Chemical compound NN1NNC=C1 PVPTUASRAVWKGX-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- KDKIWFRRJZZYRP-UHFFFAOYSA-N 1-hydroxypropane-2-sulfonic acid Chemical compound OCC(C)S(O)(=O)=O KDKIWFRRJZZYRP-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- YTQQIHUQLOZOJI-UHFFFAOYSA-N 2,3-dihydro-1,2-thiazole Chemical class C1NSC=C1 YTQQIHUQLOZOJI-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- ZWLIPWXABAEXNY-UHFFFAOYSA-N 2-hydroxydecane-1-sulfonic acid Chemical compound CCCCCCCCC(O)CS(O)(=O)=O ZWLIPWXABAEXNY-UHFFFAOYSA-N 0.000 description 1
- CZFRHHAIWDBFCI-UHFFFAOYSA-N 2-hydroxyhexane-1-sulfonic acid Chemical compound CCCCC(O)CS(O)(=O)=O CZFRHHAIWDBFCI-UHFFFAOYSA-N 0.000 description 1
- RIYJUQDMHMUBMK-UHFFFAOYSA-N 2-hydroxypentane-1-sulfonic acid Chemical compound CCCC(O)CS(O)(=O)=O RIYJUQDMHMUBMK-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- VZWOXDYRBDIHMA-UHFFFAOYSA-N 2-methyl-1,3-thiazole Chemical compound CC1=NC=CS1 VZWOXDYRBDIHMA-UHFFFAOYSA-N 0.000 description 1
- XPQIPUZPSLAZDV-UHFFFAOYSA-N 2-pyridylethylamine Chemical compound NCCC1=CC=CC=N1 XPQIPUZPSLAZDV-UHFFFAOYSA-N 0.000 description 1
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
- YEGPVWSPNYPPIK-UHFFFAOYSA-N 4-hydroxybutane-1-sulfonic acid Chemical compound OCCCCS(O)(=O)=O YEGPVWSPNYPPIK-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
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- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- UCYLTILFFMVAKP-UHFFFAOYSA-N P(=O)(O)(O)C(C(C(=O)O)(C(=O)O)C(=O)O)CC.P(O)(O)=O Chemical compound P(=O)(O)(O)C(C(C(=O)O)(C(=O)O)C(=O)O)CC.P(O)(O)=O UCYLTILFFMVAKP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
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- OHKKBBPYBGVKAI-UHFFFAOYSA-N acetic acid;n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCNCCNCCN OHKKBBPYBGVKAI-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229960003330 pentetic acid Drugs 0.000 description 1
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明所提供的蝕刻液組成物,係能形成由蝕刻所形成細線的窄寬度小、抑制細線上部出現1~5μm左右大小的缺損、具所需寬度的細線,供對銅系層施行蝕刻用。本發明所提供的蝕刻液組成物,係供對銅系層施行蝕刻用的蝕刻液組成物,含有:(A)過氧化氫0.1~35質量%;(B)羥基烷烴磺酸0.1~20質量%;(C)從唑系化合物、及構造中具有含1個以上氮原子且具3個雙鍵之雜六元環的化合物中選擇至少1種化合物0.01~1質量%;及水;且25℃的pH在0.1~4範圍內。
Description
本發明係關於供蝕刻銅系層用的蝕刻液組成物、及使用其的蝕刻方法。
表面有形成電路佈線的印刷電路板(或膜)廣泛被使用於供安裝例如電子零件、半導體元件等。而,近年隨電子機器的小型化及高機能化要求,相關印刷電路板(或膜)的電路佈線亦期待、高密度化及薄型化。又,隨智慧手機的普及,靜電容式觸控板的需求正擴大中,供對透明導電膜所使用銦-錫氧化物(以下亦稱「ITO」)薄膜,施行加工用的蝕刻液需求亦隨之提高。尤其強烈渴求對ITO薄膜上的銅及銅合金被膜,能進行選擇性蝕刻的蝕刻液。
關聯習知技術,專利文獻1所提案的蝕刻液係含有:過氧化氫、未含氟原子的酸、氟離子供應源、膦酸類、過氧化氫安定劑、及水,且pH5以下。又,專利文獻1的比較例2與5有例示由過氧化氫與5-胺基-1H-四唑組合的組成物。但,比較例2與5所例示的組成物並無法充分抑制對IGZO造成損壞,且若溶解銅等金屬化合物,便會導致過氧化氫的分解速度提升,故而並不適用為銅或以銅為主成 分的金屬化合物用蝕刻液。
再者,專利文獻2所提案的銅或銅合金用蝕刻液,係含有:鏈狀烷醇胺、分子內具酸基的螯合劑、及過氧化氫。
[專利文獻1]日本專利特開2016-111342號公報
[專利文獻2]日本專利特開2013-076119號公報
若使用專利文獻1所提案的蝕刻液對銅層施行蝕刻,則細線的粗細較大,較難獲得所需寬度的細線。尤其會有非常難形成10~40μm寬度的細線、細線上部容易出現1~5μm左右大小的缺損等問題。
緣是,本發明係為解決上述問題而完成,課題在於提供:能形成由蝕刻所形成細線的窄寬度小、抑制細線上部出現1~5μm左右大小的缺損、具所需寬度的細線,供對銅系層施行蝕刻用的蝕刻液組成物。又,本發明課題在於提供:使用上述蝕刻液組成物的蝕刻方法。
本發明者等為解決上述問題經深入鑽研,結果發現含有特定成分的蝕刻液組成物便可解決上述問題,遂完成本發明。
即,根據本發明所提供的蝕刻液組成物,係供對銅系層施行蝕刻用的蝕刻液組成物,含有:(A)過氧化氫0.1~35質量%;(B)羥基烷烴磺酸(hydroxy alkane sulfonate)0.1~20質量%;(C)從唑系化合物、及構造中具有含1個以上氮原子且具3個雙鍵之雜六元環的化合物中選擇至少1種化合物0.01~1質量%;及水;且25℃的pH在0.1~4範圍內。
本發明中,較佳係更進一步含有:(D)從下述一般式(1)所示化合物、牛磺酸、及甘胺酸所構成群組中選擇至少1種。
再者,根據本發明所提供的蝕刻方法,係包括有:使用上述蝕刻液組成物,對銅系層施行蝕刻的步驟。
根據本發明可提供:能形成由蝕刻所形成細線的窄寬度小、抑制細線上部出現1~5μm左右大小的缺損、具所需寬度的細線,供 對銅系層施行蝕刻用的。又,根據本發明可提供:使用上述蝕刻液組成物的蝕刻方法。即便使用本發明的蝕刻液組成物,但氧化銦系層仍實質不會被蝕刻。所以,本發明的蝕刻液組成物頗適用於針對含有氧化銦系層與銅系層的積層體中,僅對銅系層施行蝕刻的情況。
以下,針對本發明實施形態進行具體說明。本說明書中所謂「蝕刻」係指利用化學藥物等的腐蝕作用之塑形或表面加工技法。本發明蝕刻液組成物的具體用途係可舉例如:去除劑、表面平滑劑、表面粗化劑、圖案形成用藥劑、基體上微量附著成分的洗淨液等。本發明的蝕刻液組成物因為銅系層的除去速度快速,故頗適用為去除劑。又,若使用於具3次元構造微細形狀圖案的形成,便可獲得矩形等所需形狀的圖案,所以亦頗適用為圖案形成用藥劑。
本說明書的「銅系層」係在含銅的層之前提下,其餘並無特別的限定。「銅系層」具體係由從金屬銅、及銅鎳合金等銅合金中選擇至少1種所構成層的總稱。「銅系層」的具體例係可例如含有銅達10質量%以上的導電層。
再者,本說明書的「氧化銦系層」係在含有氧化銦的層之前提下,其餘並無特別的限定。「氧化銦系層」係例如從氧化銦、銦-錫 氧化物、及銦-鋅氧化物中選擇1種以上所構成層的總稱。
本發明的蝕刻液組成物係含有(A)過氧化氫(以下亦稱「(A)成分」)。蝕刻液組成物中的(A)成分濃度係0.1~35質量%範圍。若(A)成分的濃度未滿0.1質量%,則蝕刻速度過於緩慢,導致生產性明顯降低。另一方面,若(A)成分的濃度超過35質量%,則會有蝕刻液組成物處置困難的情況。
(A)成分的濃度係只要配合屬於被蝕刻體的銅系層之厚度、寬度,在上述濃度範圍內適當調整便可。其中,就從在可控制蝕刻速度的範圍內較快速、光阻寬度與所形成細線寬度的誤差小、細線能形成所需寬度、且能更加抑制細線上部出現1~5μm左右大小缺損的觀點,(A)成分的濃度較佳係1~20質量%範圍、更佳係1~10質量%範圍、特佳係1~5質量%範圍。
本發明的蝕刻液組成物係含有:(B)羥基烷烴磺酸(以下亦稱「(B)成分」)。蝕刻液組成物中的(B)成分濃度係0.1~20質量%範圍。若(B)成分的濃度未滿0.1質量%,便會有無法對銅系層施行蝕刻的情況。另一方面,即便(B)成分的濃度超過20質量%,但仍無法更加提升效果。(B)成分的濃度係只要配合屬於被蝕刻體的銅系層之厚度、寬度,在上述濃度範圍內適當調整便可。其中,(B)成分的濃度較佳係1~10質量%範圍。
羥基烷烴磺酸的具體例係可舉例如:2-羥基乙烷-1-磺酸 (isethionic acid、2-羥乙磺酸)、2-羥基丙烷-1-磺酸、1-羥基丙烷-2-磺酸、3-羥基丙烷-1-磺酸、2-羥基丁烷-1-磺酸、4-羥基丁烷-1-磺酸、2-羥基戊烷-1-磺酸、2-羥基己烷-1-磺酸、及2-羥基癸烷-1-磺酸、以及該等的銨鹽、鈉鹽、鉀鹽、鈣鹽、銅鹽、及鐵鹽等。其中,若使用2-羥基乙烷-1-磺酸,則即便銅系層含有氧化銅的情況,仍可依充分速度施行蝕刻,故屬較佳。
本發明的蝕刻液組成物係含有從:(i)唑系化合物、及(ii)構造中具有含1個以上氮原子且具3個雙鍵之雜六元環的化合物中選擇至少1種的化合物(以下亦稱「(C)成分」)。蝕刻液組成物中的(C)成分濃度係0.01~1質量%範圍。(C)成分的濃度係只要配合屬於被蝕刻體的銅系層之厚度、寬度,在上述濃度範圍內適當調整便可。其中,就從光阻寬度與所形成細線寬度的誤差小、細線能形成所需寬度、且能更加抑制細線上部出現1~5μm左右大小缺損的觀點,(C)成分的濃度較佳係0.01~0.5質量%。
(i)唑系化合物係例如構造中具有含1個以上氮原子且具2個雙鍵之雜五元環的化合物。唑系化合物的具體例係可舉例如:1-甲基吡咯等烷基吡咯;吡咯等唑化合物;1-甲基咪唑等烷基咪唑;腺嘌呤、咪唑、吡唑等二唑化合物;1,2,4-三唑、5-甲基-1H-苯并三唑、1H-苯并三唑、3-胺基-1H-三唑等三唑化合物;1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑(以下亦稱「5-胺基四唑」)等四唑化合物;1,3-噻唑、4-甲基噻唑、異噻唑等噻唑化合物;異唑等唑化合物。其中,若使用5-胺基四唑,則可形成頸縮更少、 且直線性更佳的細線,故屬較佳。
(ii)構造中具有含1個以上氮原子且具3個雙鍵之雜六元環的化合物具體例,係可舉例如:2-甲基吡啶等烷基吡啶化合物;2-胺基吡啶、2-(2-胺乙基)吡啶等胺基吡啶化合物;吡啶、吡、嘧啶、嗒、三、四(tetrazine)等。
本發明蝕刻液組成物在25℃下的pH係在0.1~4範圍內、較佳係1~3範圍內、更佳係1~2範圍內。
本發明的蝕刻液組成物較佳係更進一步含有:(D)從下述一般式(1)所示化合物、牛磺酸、及甘胺酸所構成群組中選擇至少1種(以下亦稱「(D)成分」)。藉由含有(D)成分,便可大幅抑制細線上部出現1~5μm左右大小的缺損。
一般式(1)中,X1及X2所示碳原子數1~5之烷二基,係可例如:亞甲基、伸乙基、伸丙基、甲基伸乙基、伸丁基、1-甲基伸丙基、2-甲基伸丙基等。一般式(1)所示化合物中,若使用n=0且X2為伸乙基的化合物、或X1與X2均為伸乙基的化合物,則抑制細線上部 出現1~5μm左右大小缺損的效果特高,故屬較佳。
本發明的蝕刻液組成物係除(A)成分、(B)成分、及(C)成分之外,尚含有必要成分之屬於溶劑的水。又,在本發明的蝕刻液組成物中,除(A)成分、(B)成分、(C)成分、及水以外的成分,在不致阻礙本發明效果之範圍內,亦可摻合周知添加劑。添加劑係可舉例如:蝕刻液組成物的安定化劑、各成分的可溶化劑、消泡劑、pH調整劑、比重調整劑、黏度調整劑、濕潤性改善劑、螯合劑、氧化劑、還原劑、界面活性劑等。該等添加劑的濃度一般係0.001~50質量%範圍。
pH調整劑係可舉例如:磷酸鈉、磷酸氫鈉等無機酸及該等的鹽;水溶性有機酸及該等的鹽;氫氧化鋰、氫氧化鈉、氫氧化鉀等氫氧化鹼金屬類;氫氧化鈣、氫氧化鍶、氫氧化鋇等氫氧化鹼土族 金屬類;碳酸銨、碳酸鋰、碳酸鈉、碳酸鉀等鹼金屬的碳酸鹽類;碳酸氫鈉、碳酸氫鉀等碳酸氫鹼金屬鹽;氫氧化四甲銨、膽鹼等氫氧化四級銨類;乙胺、二乙胺、三乙胺、羥乙胺、烷醇胺等有機胺類;麩胺酸、天冬胺酸等胺基酸;氨、氟化銨;酸性氟化銨、氫氟化銨、酸性氫氟化銨、氫氧化銨、銨碳酸鹽、碳酸氫銨鹽等。該等pH調整劑係可單獨使用1種、或組合使用2種以上。若pH調整劑係使用磷酸鈉或酸性氫氟化銨,便可形成更少缺損的細線,故屬較佳。
螯合劑係可舉例如:伸乙二胺四乙酸、二伸乙基三胺五乙酸、三伸乙基四胺六乙酸、四伸乙基五胺七乙酸、五伸乙基六胺八乙酸、氮基三乙酸、及該等的鹼金屬(較佳為鈉)鹽等胺基羧酸系螯合劑;羥基亞乙基二膦酸、氮基三亞甲基膦酸、膦醯基丁烷三羧酸、及該等的鹼金屬(較佳為鈉)鹽等膦酸系螯合劑;草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、蘋果酸、酒石酸、檸檬酸、該等的酸酐、及該等的鹼金屬(較佳為鈉)鹽等二元以上羧酸化合物、或者由二元以上羧酸化合物施行脫水的單酐或二酐。該等螯合劑的濃度一般係0.01~40質量%範圍。
蝕刻速度較快速的情況,最好將還原劑使用為添加劑。還原劑的具體例係可例如:氯化銅、氯化亞鐵、銅粉、銀粉等。該等還原劑的濃度一般係0.01~10質量%範圍。
本發明的蝕刻方法係包括有:使用上述本發明蝕刻液組成物, 對銅系層施行蝕刻的步驟。對銅系層施行蝕刻的方法並無特別的限定,採用一般的蝕刻方法便可。可舉例如利用浸漬式、噴霧式、旋轉式等施行的蝕刻方法。例如利用浸漬式的蝕刻方法,便假設在PET基板上已形成有CuNi/Cu/ITO層的基材中,僅針對CuNi/Cu層施行蝕刻的情況。此情況,在適當蝕刻條件下,將上述基材浸漬於蝕刻液組成物中之後,再上拉,便可僅針對PET基板上的CuNi/Cu層施行蝕刻。
浸漬式蝕刻方法時的蝕刻條件並無特別的限定,可配合基材(被蝕刻體)的形狀、膜厚等再行任意設定。例如蝕刻溫度較佳係設為10~60℃、更佳係20~50℃。蝕刻液組成物的溫度會因反應熱而上升。所以,視需要亦可依將蝕刻液組成物的溫度維持於上述範圍內的方式,利用公知手段進行溫度控制。又,蝕刻時間係只要設為能完成蝕刻的充分時間便可,並無特別的限定。例如電子電路基板的佈線製造時,若膜厚5~500nm左右,則只要依上述溫度範圍施行10~600秒左右的蝕刻便可。
本發明的蝕刻液組成物、及使用該蝕刻液組成物的蝕刻方法,主要係可適當使用於例如:液晶顯示器、電漿顯示器、觸控板、有機EL、太陽電池、照明器具等的電極、佈線施行加工時。
以下,利用實施例與比較例,針對本發明進行更詳細說明,惟本發明並不因該等而受限定。
依成為表1所示配方的方式,將各成分施行混合而獲得蝕刻液組成物(實施例組成物No.1~10)。另外,依成分合計成為100質量%的方式摻合水。相關實施例組成物No.1~7,pH調整劑係使用酸性氫氟化銨。
依成為表2所示配方的方式,將各成分施行混合而獲得蝕刻液 組成物(比較組成物1~3)。另外,依成分合計成為100質量%的方式摻合水,pH調整劑係使用酸性氫氟化銨。
在厚度200μm的PET基體上依序積層ITO層(50nm)、Cu層(200nm)、及CuNi層(30nm)的基體上,使用液狀光阻形成寬10μm、開口部10μm的光阻圖案。將已形成有光阻圖案的基體裁剪為長20mm×寬20mm而獲得測試片。針對所獲得測試片,使用實施例組成物No.1~10,在35℃、1分鐘、攪拌下,依浸漬式施行圖案蝕刻(蝕刻處理)。
除使用比較組成物1~3之外,其餘均依照與上述實施例11~20同樣,利用浸漬式施行圖案蝕刻。
在厚度200μm的PET基體上依序積層ITO層(50nm)、Cu層(200nm)、及CuNi層(30nm)的基體上,使用乾膜光阻形成寬10μm、開口部10μm的光阻圖案。將已形成有光阻圖案的基體裁剪為長20mm×寬20mm而獲得測試片。針對所獲得測試片,使用實施例組成物No.1~10,在35℃、1分鐘、攪拌下,依浸漬式施行圖案蝕刻(蝕刻處理)。
使用雷射顯微鏡,針對細線狀態、及光阻圖案寬度與細線寬度的誤差施行評價。相關細線狀態係利用確認細線上部有無特定長度缺損進行評價。具體而言,將無法確認到0.5μm以上長度缺損者評為「++」,可確認到0.5μm以上且未滿1μm長度缺損者評為「+」,可確認到1μm以上長度缺損者評為「-」。
再者,相關光阻圖案寬度與細線寬度的誤差,係計算出蝕刻處理前的光阻圖案寬度、與所形成細線上部的寬度間之差絕對值「L1」進行評價。「L1」值為「0」的情況,蝕刻處理前的光阻圖案寬度、與所形成細線寬度相同,意味著形成所需寬度的細線。另一方面,「L1」值越大,則意味著蝕刻處理前的光阻圖案寬度、與所形成細線寬度的差越大,並未形成所需寬度的細線。而,當「L1」值未滿0.5μm的情況評為「+++」,「L1」值為0.5μm以上且未滿1μm的情況評為「++」,「L1」值為1μm以上且未滿2μm的情況評為「+」,「L1」值達2μm以上的情況評為「-」。評價結果係如表3所示。
由表3所示結果得知,實施例11~30的細線狀態均呈良好。其中,可確認到實施例18~20及28~30所獲得細線狀態特別良好。又,得知實施例11~30的「L1」值均小,可形成所需寬度的細線。其中,得知實施例18、20、28及30的「L1」值更小,而實施例18及28的「L1」值特別小。
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